Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

The invention claimed is: 
     
       1. A compound of the formula (1), 
       
         
           
           
               
               
           
         
         where the following applies to the symbols and indices used: 
         Ar is, identically or differently on each occurrence, an aromatic ring system selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene, dibenzofuran and dibenzothiophene, each of which is optionally substituted by one or more radicals R 1 ; 
         Ar 1  and Ar 2  are, identically or differently on each occurrence, selected from the groups of the formulae (5) to (28), 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         where the dashed bond indicates the position of the bond to the nitrogen; 
         R is on each occurrence, identically or differently, and are H, D, F, Cl, Br, I, CN, Si(R 2 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where in each case one or more non-adjacent CH 2  groups is optionally replaced by Si(R 2 ) 2 , C═NR 2 , P(═O)(R 2 ), SO, SO 2 , NR 2 , O, S or CONR 2  and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene, dibenzofuran and dibenzothiophene, which may in each case be substituted by one or more radicals R 2 , or a combination of two, three, four or five of these groups, which may in each case be identical or different, an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , where two or more adjacent substituents R or two or more adjacent substituents R 1  may optionally form a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R 2 ; 
         R 1  are on each occurrence, identically or differently, and are H, D, F, CN, a straight-chain alkyl having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, or an aromatic or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, dibenzofuran and dibenzothiophene, or a combination of two, three, four or five of these groups, which may in each case be identical or different; 
         R 2  is on each occurrence, identically or differently, is H, D, F, Cl, Br, I, Si(R 3 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 3 , where one or more non-adjacent CH 2  groups is optionally replaced by Si(R 3 ) 2 , C═NR 3 , P(═O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3  and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene or a combination of two, three, four or five of these groups, which may in each case be identical or different, which may in each case be substituted by one or more radicals R 3 , an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , or an aralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , where two or more adjacent substituents R 2  may optionally form a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R 3 ; 
         R 3  is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic ring system having 6 to 30 C atoms, in which one or more H atoms is optionally replaced by D or F, where two or more adjacent substituents R 3  may form a mono- or polycyclic, aliphatic ring system with one another; 
         m is 0, 1, 2 or 3; 
         n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; 
         p is 0, 1 or 2; 
         the following compounds are excluded from the invention: 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       2. The compound according to  claim 1  of the formula (2), formula (3a), (3b), (4a) or formula (4b), 
       
         
           
           
               
               
           
         
         where the symbols and indices used have the meanings given in  claim 1 . 
       
     
     
       3. The compound according to  claim 1 , wherein the groups Ar 1  and Ar 2  are selected, identically or differently on each occurrence, from the groups of the formulae (5a) to (28a), 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         where the symbols used have the meanings given in  claim 1 , and the dashed bond indicates the position of the bond from the group to the nitrogen. 
       
     
     
       4. The compound according to  claim 1 , wherein Ar 1  is a group of the formula (6), (7), (8), (9) or (21). 
     
     
       5. The compound according to  claim 3 , wherein Ar 1  is a group of the formula (6a), (7a), (8a), (9a) or (21a). 
     
     
       6. The compound according to  claim 1 , wherein the groups Ar 1  and Ar 2  are different from one another. 
     
     
       7. A compound of the formula (1), 
       
         
           
           
               
               
           
         
         where the following applies to the symbols and indices used: 
         Ar is, identically or differently on each occurrence, an aromatic ring system selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene, dibenzofuran and dibenzothiophene, each of which is optionally substituted by one or more radicals R 1 ; 
         the group —NAr 1 Ar 2  has the structure of one of the formulae (29), (30), (31) or (32) or in that the group —Ar—NAr 1 Ar 2  has the structure of one of the formulae (33), (34), (35) or (36), 
       
       
         
           
           
               
               
           
         
         and the dashed bond indicates the bond to the spirobifluorene or to Ar; 
       
       
         
           
           
               
               
           
         
         and the dashed bond indicates the bond to the spirobifluorene; 
         where 
         R is on each occurrence, identically or differently, and are H, D, F, Cl, Br, I, CN, Si(R 2 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where in each case one or more non-adjacent CH, groups is optionally replaced by Si(R 2 ) 2 , C═NR 2 , P(═O)(R 2 ), SO, SO 2 , NR 2 , O, S or CONR 2  and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene, dibenzofuran and dibenzothiophene, which may in each case be substituted by one or more radicals R 2 , or a combination of two, three, four or five of these groups, which may in each case be identical or different, an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , where two or more adjacent substituents R or two or more adjacent substituents R 1  may optionally form a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R 2 ; 
         R 1  are on each occurrence, identically or differently, and are H, D, F, CN, a straight-chain alkyl having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, or an aromatic or heteroaromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, dibenzofuran and dibenzothiophene, or a combination of two, three, four or five of these groups, which may in each case be identical or different; 
         R 2  is on each occurrence, identically or differently, is H, D, F, Cl, Br, I, Si(R 3 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 3 , where one or more non-adjacent CH 2  groups is optionally replaced by Si(R 3 ) 2 , C═NR 3 , P(═O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3  and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic ring system having 6 to 60 C atoms selected from the group consisting of benzene, naphthalene, phenanthrene, fluorene, spirobifluorene or a combination of two, three, four or five of these groups, which may in each case be identical or different, which may in each case be substituted by one or more radicals R 3 , an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , or an aralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , where two or more adjacent substituents R 2  may optionally form a mono- or polycyclic, aliphatic ring system, which is optionally substituted by one or more radicals R 3 ; 
         R 3  is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic ring system having 6 to 30 C atoms, in which one or more H atoms is optionally replaced by D or F, where two or more adjacent substituents R 3  may form a mono- or polycyclic, aliphatic ring system with one another; 
         m is 0, 1, 2 or 3; 
         n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; 
         p is 0, 1 or 2; and 
         the following compounds are excluded from the invention: 
       
       
         
           
           
               
               
           
         
       
     
     
       8. The compound according to  claim 1 , wherein the group —(Ar) p — stands for a group of one of the formulae (37) to (50), 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         where the symbols used have the meanings given in  claim 1 , and one dashed bond indicates the bond to the spirobifluorene and the other dashed bond indicates the bond to the nitrogen atom. 
       
     
     
       9. A process for the preparation of the compound according to  claim 1  which comprises coupling a spirobifluorene derivative which is substituted in the 2-position by a reactive leaving group to
 a) a primary amine, followed by coupling to a further aromatic group which is substituted by a reactive leaving group, or 
 b) to a secondary amine, or 
 c) to a triarylamine derivative. 
 
     
     
       10. A formulation, comprising at least one compound according to  claim 1  and at least one solvent. 
     
     
       11. A solution, dispersion or mini-emulsion comprising at least one compound according to  claim 1  and at least one organic solvent. 
     
     
       12. A mixture comprising at least one compound according to  claim 1  and at least one further compound. 
     
     
       13. An electronic device comprising the compound according to  claim 1 . 
     
     
       14. An electronic device comprising the formulation according to  claim 10 . 
     
     
       15. The electronic device according to  claim 13 , wherein the electronic device is an organic electroluminescent device (organic light-emitting diode, OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitised solar cell (ODSSC), an organic optical detector, an organic photoreceptor, na organic field-quench device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) or an organic plasmon emitting device. 
     
     
       16. The electronic device according to  claim 14 , wherein the electronic device is an organic electroluminescent device (organic light-emitting diode, OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitised solar cell (ODSSC), an organic optical detector, an organic photoreceptor, na organic field-quench device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) or an organic plasmon emitting device. 
     
     
       17. An organic electroluminescent device comprising the compound according to  claim 1  is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking layer or as matrix material for fluorescent or phosphorescent emitters. 
     
     
       18. An organic electroluminescent device comprising the mixture according to  claim 12  is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking layer or as matrix material for fluorescent or phosphorescent emitters. 
     
     
       19. The compound according to  claim 1 , wherein
 R 3  is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic ring system having 6 to 30 C atoms, in which one or more H atoms is optionally replaced by D or F. 
 
     
     
       20. The compound according to  claim 1 , wherein
 R 1  is identically, or differently, on each occurrence selected from the group consisting of H or D, a straight-chain alkyl having 1 to 10 C atoms, and a branched or cyclic alkyl group having 3 to 10 C atoms. 
 
     
     
       21. The compound according to  claim 7 , wherein
 R 1  is identically, or differently, on each occurrence selected from the group consisting of H or D, a straight-chain alkyl having 1 to 10 C atoms, and a branched or cyclic alkyl group having 3 to 10 C atoms.